Organic ligands containing terpyridine and disulfide groupings linked between one another by a bonding -O(CH 2 ) n -(n = 6, 12) fragment have been synthesized. Gold nanoparticles of mean size 1.8 nm modified with the indicated ligand were obtained by the method of Brust. By methods of electron spectroscopy and cyclic voltamperometry, the possibility of forming of coordinated compounds on the surface of gold nanoparticles modified by a terpyridine ligand, on interaction with Cu(MeCN) 4 ClO 4 has been shown. The obtained nanoparticles catalyze the oxidation of 2,4-di-tert-butylphenol into 3,3',5,5'-tetra(tert-butyl)biphenyl-2,2'-diol.The search for low molecular analogs of natural metalloenzymes as catalysts of organic reactions is an urgent problem of contemporary bioinorganic chemistry. Copper-containing redox-enzymes of type 3 (hemocyanine, tyrosinase, and catechol oxidase) are capable of reversibly binding molecular oxygen, fulfilling in the animal organism the function of transferers of oxygen (hemocyanine), catalysts of phenolic hydroxylation in the o-position (tyrosinase) or oxidation of pyrocatechols into the corresponding o-quinones (catechol oxidase) [1-3]. The first attempts to imitate the monooxygenase activity of type 3 copper-containing enzymes were undertaken in the fifties of the twentieth century [4]. It was then discovered that the simplest salts of monovalent copper were capable of catalyzing the oxidation of phenols. Later, similar catalytic activity was shown for coordination compounds of Cu(I) with pyridine and phenanthroline [5][6][7][8]. However, as a rule, the reactions led to the formation of mixtures of products and the mechanism of carrying out the conversions remained unclear. For example it was shown at the same time that copper(I) complexes with organic ligands were capable of catalyzing the oxidation of pyrocatechols to o-quinones [6]. Later Karlin and co-workers [9-11] synthesized a series of binuclear coordination compounds of copper with trimethylpyridylamine (TMPA) and _______ * Dedicated to Academician of the Russian Academy of Sciences N. S. Zefirov on the occasion of his jubilee.
: As the development of available binder in the harsh conditions is needed, we propose the proper binder for high-voltage lithium-ion secondary batteries based on the quantum chemistry modeling. The optimized structures, HOMO (Highest Occupied Molecular Orbital) energies and ionization potentials of 4 binders, which were considered from monomer to tetramer, were investigated by the semi-empirical and DFT (Density Functional Theory) calculations. The results show that the ionization potential values by calculation tend to be close to the oxidation potentials from the measurement of linear sweep voltametry (LSV). The order of oxidative resistance from high value to low value is following: poly(hexafluropropylene), poly(vinylidene fluoride), poly(methyl acrylate) and poly(acryl amide). Also these results correspond with the experimental values. Thus, we find the reason why HOMO (Highest Occupied Molecular Orbital) energy of PHFP has the highest value than other binders by analysis of HOMO orbital structures.
A series of novel organic ligands with dipicolylamine and disulfide groups connected by polymethylene, alkylaryl, alkoxyaryl, or alkoxycarbonyl linker was synthesized. The electro chemical study by cyclic voltammetry was carried out for two synthesized ligands, and the formation of the complexes with Cu(MeCN)ClO 4 in the solution or on the gold electrode surface was established. The complex of Cu I with 1,24 bis[N,N bis(2 pyridylmethyl) glycinoyloxy] 12,13 dithiatetracosane chemisorbed on the Au electrode is capable of binding molecular oxygen from solution.
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